CN102061197A - Coke oven gas desulfuration and deamination combined purifying method and special device thereof - Google Patents
Coke oven gas desulfuration and deamination combined purifying method and special device thereof Download PDFInfo
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- CN102061197A CN102061197A CN2011100255825A CN201110025582A CN102061197A CN 102061197 A CN102061197 A CN 102061197A CN 2011100255825 A CN2011100255825 A CN 2011100255825A CN 201110025582 A CN201110025582 A CN 201110025582A CN 102061197 A CN102061197 A CN 102061197A
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Abstract
The invention discloses a coke oven gas desulfuration and deamination combined purifying method and a special device thereof. The method comprises a desulfuration method and a deamination method; coke oven gas desulfuration adopts a wet type catalytic oxidation method, and deamination adopts a water washing method; coke oven gas is subjected to cooling naphthalene scrubbing before being desulfurized and then desulfurized; the coke oven gas is subjected to the water washing method deamination and ammonia evaporation after being desulfurized; and ammonia consumed by desulfuration is derived from ammonia generated by gas and ammonia evaporation. The special device comprises an oil naphthalene scrubbing precooling tower, a desulfurizing tower, an ammonia water washing tower and an ammonia evaporating tower which are connected in sequence. The combined process disclosed in the invention has the characteristics of high efficiency, energy saving, lower investment and lower operating cost. The concentrated ammonia water circulating process has the function of adsorbing and removing hydrogen sulfide. The desulfuration and deamination combined process has the effect of desulfuration twice. In addition, a gas naphthalene scrubbing precooling tower adopted by the process of the invention has the functions of scrubbing naphthalene and cooling gas, and the naphthalene scrubbing adopts a way of combining spraying absorption, liquid film absorption and cooling, thereby improving the naphthalene scrubbing and precooling effect.
Description
Technical field
The present invention relates to a kind of purifying method and isolated plant thereof of coke-oven gas, relate in particular to a kind of purifying method and isolated plant thereof of coke oven gas desulfurization deamination associating.
Background technology
At present, the main application of coke-oven gas comprises as Lu Kiln heating fuel with as the chemical industry raw material of synthetic gas and using.When using, require H as stove Kiln fuel
2S content must not surpass 200mg/m
3When using, require H as the chemical industry raw material of synthetic gas
2S content must not surpass 0.1mg/m
3Therefore, coke-oven gas will adopt sulfur removal technology to carry out could using after desulfurization is handled.Before the eighties in last century, the coke-oven plant of domestic construction does not all have the coal gas desulfurization device, the beginning of the eighties in last century so far, all synchronized constructions or reconstructed the sulfur removal technology system later on when founding the factory of domestic most of coke-oven plants.
No matter coke-oven plant's desulphurization technological process is the external Technology of introducing, or the Technology of domestic-developed, and common characteristic is: employing is that the catalytic oxidation sulfur removal technology of alkali source combines with chemical absorption method deamination technology with ammonia, uses together.FRC sulfur removal technology and phosphorus ammonium method deamination production anhydrous ammonia technology as Baosteel coal gas refinery link; T-H sulfur removal technology and saturex method sulphur ammonium production technique link; The HPF sulfur removal technology of domestic-developed is to produce thiamine process with the saturex method to link all.The sulfur removal technology that has combines not only reasonable but also has complementarity with the production of sulphur ammonium, combine with sulphur ammonium production technique as the T-H method; The FRC sulfur removal technology is produced anhydrous ammonia technology with phosphorus ammonium method and is combined.But other bonded processing methodes have not just had rational complementary characteristic.If any regional soil belong to acid geology, should not adopt thiamine fertilizer.Yet, HPF sulfur removal technology and other vacuum salt of wormwood methods, Sol Fei Banfa desulfurization all is to combine with chemical absorption method deamination (producing or the anhydrous ammonia production technique as the sulphur ammonium).The shortcoming of this strap-on combined technique makes the coke-oven plant can not independently select products scheme, easily causes products and marketing to deviate from mutually.In addition, ammonium sulfate products does not belong to the high-quality chemical fertilizer in agrochemical, and nitrogen content is no more than 21.21%.Other parts are useless acidic substance part.So the production cost height, technology motor machine total installation of generating capacity is big, and sulfuric acid consumption is big, and the device material requires to adopt the corrosion resistant material.Engineering construction cost is bigger.
In a word, adopt the catalytic oxidation desulfurization technology that combines with the production of sulphur ammonium, its advantage is the desulfuration efficiency height, deamination efficient height.But the shortcoming of this array mode is a sulphur ammonium production cost height, and produce market is limited by area feature.In addition, the ammonia process of desulfurization will be cooled to coal gas to absorb operation below 30 ℃, and enters sulphur ammonium production equipment after again coal gas being heated to 65～70 ℃ after the desulfurization operations.Behind the sulphur ammonium production equipment, gas temperature rises.To require that coal gas is carried out end before inhaling the benzene tower again cold entering.Therefore, the energy utilization of this process combination mode is unreasonable.The energy consumption height is maximum shortcoming.
It is to have advantages such as efficient, energy-conservation, low cost, high benefit, short flow process that modern coking enterprise requires gas purification process.
The domestic AS sulfur removal technology of introducing in recent years.Have reasonably energy utilization characteristics, full negative pressure technical process does not need to establish intercooling and final cooling.The malleation technical process is only established once cold eventually.But the main drawback of AS sulfur removal technology is that desulfuration efficiency is low than catalytic oxidation, has only 75%～80% of catalytic oxidation.Reach identical desulfuration efficiency, often need to carry out repeatedly desulfurization processing and just can reach requirement.The AS doctor treatment is obviously uneconomical.
Summary of the invention
Goal of the invention: at the deficiencies in the prior art, the purifying method that the purpose of this invention is to provide the associating of a kind of coke oven gas desulfurization deamination to realize that the catalytic oxidation desulfurizer is linked together with the washing ammonia device of circulation suction method efficiently, is formed efficiently, energy-conservation, the novel process of low consumption.Another object of the present invention provides the isolated plant of this method.
Technical scheme: in order to realize the foregoing invention purpose, the technical solution used in the present invention is:
A kind of purifying method of coke oven gas desulfurization deamination associating is characterized in that: comprise sulfur method and deamination method, coke oven gas desulfurization adopts the catalytic wet oxidation method, and deamination adopts WATER-WASHING METHOD; Cool off earlier before the coke oven gas desulfurization and wash naphthalene, water elution ammonia and ammonia still process are carried out in then desulfurization after the desulfurization; The ammonia that desulfurization consumed derives from the ammonia of coal gas and ammonia still process generation.
Described cooling is washed naphthalene and is comprised two sections of oil wash and water coolings, and oil wash comprises oil cooling and oil wash naphthalene, and water cooling is that gas liquor is direct-cooled.Described cooling is washed the naphthalene service temperature and is controlled at below 33～35 ℃.
A kind of isolated plant of purifying method of coke oven gas desulfurization deamination associating comprises the oil wash naphthalene precooling tower, thionizer, water Ammonic washing tower and the ammonia still that connect successively; Described oil wash naphthalene precooling tower is provided with precooling cyclic ammonia water water cooler; Described water Ammonic washing tower is provided with the rich ammoniacal liquor water cooler of circulation, circulation half rich ammoniacal liquor water cooler and washes ammonia water stripping water cooler; Be provided with the strong ammonia gas condensate cooler in the outlet of the top of described ammonia still, on described strong ammonia gas condensate cooler, be provided with strong aqua (vapour) pipeline and communicate with thionizer; Described water Ammonic washing tower and ammonia still connecting pipeline are provided with poor/rich ammoniacal liquor interchanger.
Described oil wash naphthalene precooling tower is made of vertical pipe type indirect cooler and direct-cooled sprinker; Washing oil washs the coal gas naphthalene simultaneously at refrigerative; The oil gas way of contact is empty spray formula, material filling type or liquid film type.
The indirect-cooling standpipe of described vertical pipe type indirect cooler is garden shape pipe or rectangular tube.
Described ammonia still is the volatile ammonia distillation tower.The distilled ammonia wastewater ammonia quantity of discharging from the volatile ammonia distillation tower is below 0.05%, and Ammonic washing tower is returned in the circulation of part distilled ammonia wastewater.
The purifying method of coke oven gas desulfurization deamination of the present invention associating is a kind ofly to be the catalytic oxidation desulfurization of alkali source with ammonia and to inhale ammonia novel process linked together with WATER-WASHING METHOD.Novel process of the present invention makes two kinds of technologies with strong complementarity, and reasonable disposition desulphurization system ammonia concentration improves desulfuration efficiency; Remove acid gas impurities in the coal gas before washing ammonia, make and wash ammonia equipment solidity to corrosion and strengthen, can save the acid gas splitter during rich ammonia distillation.A kind of new process combination flow process of the present invention can place full negative pressure system, also can place positive side.When placing full negative pressure system, only establish once just coldly, when placing the malleation side, only establish once the cold taking-up blower fan heat of compression eventually.
The isolated plant of the purifying method of coke oven gas desulfurization deamination associating of the present invention is provided with before thionizer " coal gas oil wash naphthalene-water precooling tower ", removes clean with tar, naphthalene that circulating washing oil is carried coal gas secretly; Then coal gas directly is cooled to the processing requirement temperature with the circulation weak ammonia, this temperature is set at 30 ℃.The cooling of circulation weak ammonia is cooled off with the water at low temperature water cooler.Coal gas after the precooling enters thionizer and carries out desulfurization with circulation desulfurization liquid, and coal gas desulfurization adopts catalytic oxidation, is alkali source with coking ammonia.The ammonia source is from the self-produced coal gas in coke-oven plant, strong aqua, remained ammonia.Coal gas after the desulfurization enters Ammonic washing tower and absorbs ammonia with weak ammonia or soft water.Coal gas directly enters the crude benzol absorption tower behind the Ammonic washing tower.The rich ammoniacal liquor of inhaling behind the ammonia is sent to the distillation of ammonia distillation tower, strong aqua or strong ammonia gas, part replenishes circulation desulfurization liquid, rest part can with the associating of ammonia decomposition technique, or with the anhydrous ammonia process integration, or unite with saturex sulphur ammonium production technique.Can select follow-up process integration according to market and products scheme.Waste water behind the ammonia distillation tower partly replenishes Ammonic washing tower and washes ammoniacal liquor, and remainder is arranged to biochemical sewage treatment system.
Desulfurization regeneration can be a two-tower type technology, can be a tower one slot type technology, also can be a tower technology.
Wash ammonia and can adopt a tower to wash ammonia for three sections, also can adopt two towers to wash ammonia for five sections.Washing ammonia with a tower syllogic is example, contacts the rich ammoniacal liquor of the circulation of washing ammonia at first with coal gas and tells the rich ammoniacal liquor of part send to ammonia still and make the rich ammoniacal liquor of ammonia still process raw material in circulation.Second section cyclic ammonia water of Ammonic washing tower is half rich ammoniacal liquor, tells part half rich ammoniacal liquor as first section the additional ammoniacal liquor of washing in circulation.Coal gas leaves to use from the distilled ammonia wastewater of ammonia still before the Ammonic washing tower washes ammoniacal liquor as last step, guarantee tower after the coal gas ammonia quantity less than 0.03g/m3.These three grades of circulations are washed ammoniacal liquor and are cooled off through 4 water at low temperature water coolers in circulation.
Adopt catalytic oxidation desulfurization and washing ammonia to combine, the sulfur removal technology high-level efficiency, the coal gas acid gas-containing is few, and Ammonic washing tower corrodibility is died down, and thionizer can adopt carbon steel material.In addition, wash ammonia cyclic ammonia water ammonia content between 3～9g/l, hydrogen sulfide in the coal gas is had receptivity, the residual hydrogen sulfide of coal gas is partially absorbed in washing the ammonia process behind the thionizer.Therefore be equivalent to twice desulfurization, promptly pass through catalytic oxidation desulfurization and ammoniacal liquor circulation desulfurization.If adopt three grades of desulfurization of catalytic oxidation, coal gas hydrogen sulfide is from 7000mg/m
3Drop to 20mg/m
3, desulfuration efficiency reaches 99.7%.Again hydrogen sulfide is sloughed 40% then in washing ammonia process, then the final sulfide hydrogen amount of coal gas will be less than 12mg/m
3Therefore process combination of the present invention is particularly suitable for the coke gas purification system that coke oven coal ammonia terminal is used to make synthetic gas production methyl alcohol.
Beneficial effect: compared with prior art, main contribution of the present invention has: the washing ammonia device of catalytic oxidation desulfurizer and circulation suction method is linked together efficiently, forms efficiently, and is energy-conservation, the novel process of low consumption.For sulfide hydrogen amount height and the low gas purification of ammonia quantity have can be for the scheme of optimal selection.Remove sulfide and prussiate in advance before the washing ammonia, alleviated the fixedly ammonium amount in the rich ammoniacal liquor, reduce the fixedly alkali consumption of ammonium decomposition reaction.Fundamentally overcome traditional washing ammonia-strong aqua technology and AS cyclic ammonia water sulfur removal technology and exist ammonia still process vapour to separate out sulphur for a long time, the salt blocking pipeline and the equipment of sulphur and cyanogen.And increase alkali number consumption when decomposing fixedly ammonium.Do not establish gas final cold tower (section) before the water Ammonic washing tower separately, have the ammonia of washing and whole cold-working usefulness simultaneously at the Ammonic washing tower hypomere.This end that is different from malleation AS ammoniacal liquor sulfur removal technology is cold, and the end that also is different from traditional washing ammonia process is cold.Dissolved ammonia of cold recirculated cooling water while at the end of the two kinds of technologies in back and sour gas, whole cold water row is to mechanical settling tank.And novel process of the present invention adopts whole cold water to make rich ammoniacal liquor to send distillation processing.
Description of drawings
Accompanying drawing is the structural representation of isolated plant of the present invention.
Embodiment
The present invention will be further explained below in conjunction with accompanying drawing.
Embodiment 1
A kind of purifying method of coke oven gas desulfurization deamination associating comprises sulfur method and deamination method, and coke oven gas desulfurization adopts the catalytic wet oxidation method, and deamination adopts WATER-WASHING METHOD; Cool off earlier before the coke oven gas desulfurization and wash naphthalene, water elution ammonia and ammonia still process are carried out in then desulfurization after the desulfurization; The ammonia that desulfurization consumed derives from the ammonia of coal gas and ammonia still process generation.Described cooling is washed naphthalene and is comprised two sections of oil wash and water coolings, and oil wash comprises oil cooling and oil wash naphthalene, and water cooling is that gas liquor is direct-cooled.Described cooling is washed the naphthalene service temperature and is controlled at below 33～35 ℃.
As shown in Figure 1, be the isolated plant of the purifying method of coke oven gas desulfurization deamination of the present invention associating.This isolated plant comprises oil wash naphthalene precooling tower 1, thionizer 2, water Ammonic washing tower 3 and the ammonia still 4 that connects successively; Oil wash naphthalene precooling tower 1 is provided with precooling cyclic ammonia water water cooler 5; Water Ammonic washing tower 3 is provided with the rich ammoniacal liquor water cooler 6 of circulation, circulation half rich ammoniacal liquor water cooler 7 and washes ammonia water stripping water cooler 8; Be provided with strong ammonia gas condensate cooler 9 in the outlet of the top of ammonia still 4, on strong ammonia gas condensate cooler 9, be provided with strong aqua or strong ammonia gas pipeline and communicate with thionizer 2; Water Ammonic washing tower 3 and ammonia still 4 connecting pipelines are provided with poor/rich ammoniacal liquor interchanger 10.
Oil wash naphthalene precooling tower 1 is made of vertical pipe type indirect cooler and direct-cooled sprinker; Washing oil washs the coal gas naphthalene simultaneously at refrigerative; The oil gas way of contact is empty spray formula, material filling type or liquid film type.The indirect-cooling standpipe of vertical pipe type indirect cooler is round tube or rectangular tube.
Oil wash naphthalene precooling tower 1 is set before thionizer 2, removes clean with tar, naphthalene that circulating washing oil 18 is carried coal gas 11 secretly; Then coal gas 11 usefulness circulation weak ammonias 17 directly are cooled to the processing requirement temperature.The cooling of circulation weak ammonia 17 is cooled off with water at low temperature water cooler 5.Coal gas 11 after the precooling enters thionizer 2 usefulness circulation desulfurization liquid 12 and carries out desulfurization, and catalytic oxidation is adopted in coal gas 11 desulfurization, is alkali source with coking ammonia.The ammonia source is from the self-produced coal gas in coke-oven plant, strong aqua, remained ammonia.Coal gas 11 after the desulfurization enters water Ammonic washing tower 3 usefulness weak ammonias 15 or soft water 14 absorbs ammonia.The coal gas 11 that water Ammonic washing tower 3 is discharged directly enters the crude benzol absorption tower.Rich ammoniacal liquor 20 behind the suction ammonia is sent to ammonia still 4 distillations, get strong aqua or strong ammonia gas 16, part replenishes circulation desulfurization liquid, rest part can be united with the ammonia decomposition technique, or with the anhydrous ammonia process integration, or with saturex sulphur ammonium production technique associating, can select follow-up process integration according to market and products scheme.Waste water 13 part make up water Ammonic washing towers 3 behind the ammonia still 4 are washed ammoniacal liquor, and remainder is arranged to biochemical sewage treatment system.
Desulfurization regeneration can be a two-tower type technology, can be a tower one slot type technology, also can be a tower technology.
Wash ammonia and can adopt a tower to wash ammonia for three sections, also can adopt two towers to wash ammonia for five sections.Washing ammonia with a tower syllogic is example, contacts the rich ammoniacal liquor 15 of the circulation of washing ammonia at first with coal gas and tells the rich ammoniacal liquor 20 of part send to ammonia still 4 and make the rich ammoniacal liquor of ammonia still process raw material in circulation.3 second sections cyclic ammonia waters of water Ammonic washing tower are half rich ammoniacal liquor 14, tell part half rich ammoniacal liquor as first section the additional ammoniacal liquor of washing in circulation.Use before the coal gas 11 leaving water Ammonic washing towers 3 from the distilled ammonia wastewater 13 of ammonia still 4 and wash ammoniacal liquor as last step, guarantee tower after the coal gas ammonia quantity less than 0.03g/m3.These three grades of circulations wash ammoniacal liquor in circulation through the rich ammoniacal liquor water cooler 6 of circulation, circulation half rich ammoniacal liquor water cooler 7 with wash ammonia water stripping water cooler 8 and poor/rich ammoniacal liquor interchanger 10 cools off.
Claims (8)
1. the purifying method of a coke oven gas desulfurization deamination associating is characterized in that: comprise sulfur method and deamination method, coke oven gas desulfurization employing catalytic wet oxidation method, deamination employing WATER-WASHING METHOD; Cool off earlier before the coke oven gas desulfurization and wash naphthalene, water elution ammonia and ammonia still process are carried out in then desulfurization after the desulfurization; The ammonia that desulfurization consumed derives from the ammonia of coal gas and ammonia still process generation.
2. the purifying method of coke oven gas desulfurization deamination according to claim 1 associating is characterized in that: described cooling is washed naphthalene and is comprised two sections of oil wash and water coolings, and oil wash comprises oil cooling and oil wash naphthalene, and water cooling is that gas liquor is direct-cooled.
3. the purifying method of coke oven gas desulfurization deamination associating according to claim 1 and 2, it is characterized in that: the naphthalene service temperature is washed in described cooling, washes the naphtalene oil temperature and is controlled in 30～35 ℃ of scopes, and precooling is controlled in 30 ℃.
4. the isolated plant of the purifying method of a coke oven gas desulfurization deamination associating is characterized in that: comprise the oil wash naphthalene precooling tower, thionizer, water Ammonic washing tower and the ammonia still that connect successively; Described oil wash naphthalene precooling tower is provided with precooling cyclic ammonia water water cooler; Described water Ammonic washing tower is provided with the rich ammoniacal liquor water cooler of circulation, circulation half rich ammoniacal liquor water cooler and washes ammonia water stripping water cooler; Outlet is provided with the strong ammonia gas condensate cooler on the top of described ammonia still, is provided with strong aqua or the strong ammonia gas pipeline communicates with thionizer on described strong ammonia gas condensate cooler; Described water Ammonic washing tower and ammonia still connecting pipeline are provided with poor/rich ammoniacal liquor interchanger.
5. the isolated plant of the purifying method of coke oven gas desulfurization deamination associating according to claim 4, it is characterized in that: described oil wash naphthalene precooling tower is made of vertical pipe type indirect cooler and direct-cooled sprinker; Washing oil washs the coal gas naphthalene simultaneously at refrigerative; The oil gas way of contact is empty spray formula, material filling type or liquid film type.
6. the isolated plant of the purifying method of coke oven gas desulfurization deamination associating according to claim 5 is characterized in that: the indirect-cooling standpipe of described vertical pipe type indirect cooler is garden shape pipe or rectangular tube.
7. the isolated plant of the purifying method of coke oven gas desulfurization deamination associating according to claim 4, it is characterized in that: described ammonia still is the volatile ammonia distillation tower.
8. the isolated plant of the purifying method of coke oven gas desulfurization deamination associating according to claim 7 is characterized in that: the distilled ammonia wastewater ammonia quantity of discharging from the volatile ammonia distillation tower is below 0.05%, and Ammonic washing tower is returned in the circulation of part distilled ammonia wastewater.
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| CN103146439A (en) * | 2012-12-18 | 2013-06-12 | 柳州钢铁股份有限公司 | Coke oven gas negative pressure naphthalene washing method and equipment |
| CN103663805A (en) * | 2013-12-13 | 2014-03-26 | 武汉钢铁(集团)公司 | Method and device for pretreating coal gas desulfurization waste liquid through vacuum potassium carbonate method |
| CN104479762A (en) * | 2014-11-26 | 2015-04-01 | 北京首钢国际工程技术有限公司 | Coke oven gas desulfuration alkali washing process |
| CN104629818A (en) * | 2015-02-03 | 2015-05-20 | 薛斌 | Desulfurization liquid enrichment dual-effect desorption process and system by virtue of vacuum carbonate method |
| CN106475350A (en) * | 2015-08-24 | 2017-03-08 | 鞍钢股份有限公司 | A kind of precooling tower fast sweep method |
| CN107106968A (en) * | 2014-10-28 | 2017-08-29 | 蒂森克虏伯工业解决方案股份公司 | The reduction of Naphthalene in Coke Oven Gas |
| CN107585816A (en) * | 2017-09-30 | 2018-01-16 | 江苏迈克化工机械有限公司 | A kind of low-concentration ammonia-nitrogen removes equipment |
| CN111087004A (en) * | 2019-12-23 | 2020-05-01 | 首钢水城钢铁（集团）有限责任公司 | Method for treating residual ammonia water in coal gasification production and recovery of coke oven |
| CN113801705A (en) * | 2021-09-18 | 2021-12-17 | 中国五环工程有限公司 | Atmospheric gas purification system |
| CN115414768A (en) * | 2022-08-30 | 2022-12-02 | 宝钢工程技术集团有限公司 | Device for absorbing desulfurization regeneration tail gas and ammonium phosphate and distilling ammonia and using method thereof |
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| CN103146439A (en) * | 2012-12-18 | 2013-06-12 | 柳州钢铁股份有限公司 | Coke oven gas negative pressure naphthalene washing method and equipment |
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| CN103663805A (en) * | 2013-12-13 | 2014-03-26 | 武汉钢铁(集团)公司 | Method and device for pretreating coal gas desulfurization waste liquid through vacuum potassium carbonate method |
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| CN104629818A (en) * | 2015-02-03 | 2015-05-20 | 薛斌 | Desulfurization liquid enrichment dual-effect desorption process and system by virtue of vacuum carbonate method |
| CN106475350A (en) * | 2015-08-24 | 2017-03-08 | 鞍钢股份有限公司 | A kind of precooling tower fast sweep method |
| CN106475350B (en) * | 2015-08-24 | 2018-06-26 | 鞍钢股份有限公司 | A kind of precooling tower fast sweep method |
| CN107585816A (en) * | 2017-09-30 | 2018-01-16 | 江苏迈克化工机械有限公司 | A kind of low-concentration ammonia-nitrogen removes equipment |
| CN111087004A (en) * | 2019-12-23 | 2020-05-01 | 首钢水城钢铁（集团）有限责任公司 | Method for treating residual ammonia water in coal gasification production and recovery of coke oven |
| CN113801705A (en) * | 2021-09-18 | 2021-12-17 | 中国五环工程有限公司 | Atmospheric gas purification system |
| CN115414768A (en) * | 2022-08-30 | 2022-12-02 | 宝钢工程技术集团有限公司 | Device for absorbing desulfurization regeneration tail gas and ammonium phosphate and distilling ammonia and using method thereof |
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